Carbon composition and shaped article made therefrom

ABSTRACT

Particles of carbon mixed with silicon and a bonding amount of calcium aluminate or Portland type cement. Other refractory materials and pitch may also be present. The composition is mixed with water and poured into a mold to form various shaped articles. These are set and dried sufficiently for shipment and use. The final carbon bonding takes place at high temperature use, above 2500*F, aided by carbonization of the pitch if pitch is also present.

106-97. AU 115 EX United States Patent 1 1 i 1111 3,923,531

Parsons et al. 1 1 *Dec. 2, 1975 CARBON COMPOSITION AND SHAPED 3.442.670 5/1969 Parsons 106/64 ARTICLE MADE THEREFROM 3,846,144 11/1974 Parsons ct nl 106/64 [75] Inventors: Joseph R. Parsons, Park Forest;

H [Harold L Rechter, Chicago, both of Primary Examinerl Peer Attorney, Agent, or Firm-Foster York {73] Assignee: Chicago Fire Brick Company,

Chicago. ll].

1 Notice: The portion of the term of this patent subsequent to Nov. 5, 1991, [5 B TRACT has been disclaimed.

[22] Filed; Jul 5, 1974 Particles of carbon mixed with silicon and a bonding amount of calcium aluminate or Portland type cement. Other refractory materials and pitch may also be present. The composition is mixed with water and [2]] Appl. No.: 485.964

52 us. Cl. 106/56; lO6/64; 106/97 poured into a mold to form various Shaped articles- {51 1 Int. (1 C043 7/02; C045 35/02; 045 35 52 These are set and dried sufficiently for shipment and 58 Field of Search 106/56, 64, 97 e The final Carbon bonding takes place at high perature use, above 2500F. aided by carbonization of [56) Referen Cit d the pitch if pitch is also present.

UNITED STATES PATENTS 315L813 5/1966 Cremer ct a1 106/64 6 Claims, N0 Drawings CARBON COMPOSITION AND SHAPED ARTICLE MADE THEREFROM BACKGROUND OF THE INVENTION The invention relates to carbon compositions, suitable for making carbon blocks and other shapes for refractory use; and to the shaped article made therefrom.

The invention is an improvement over the compositions and refractory articles disclosed in our US. Pat. No. 3,422,670 in that the refractory article made by the composition of this invention provides greater strength at higher temperatures than the refractory article of US. Pat. No. 3,422,670.

The castable shapes with carbon or graphite made in acafidan ce with our invention can be used in the most severe iron and steelmaking applications, such as a skimmer in a blast furnace trough or ,cupola spout, requiFirTg6nly a ;dryout,and perform cornparably to conventionally formed carbon and graphite refractories in the ability to withstand moving streams of molten iron and slags but with superior resistance to erosion and qn.--

SUMMARY OF THE INVENTION The castable formulations consist essentially of 20 to 80 per cent by weight of carbon or graphite, preferably three-fourths inch and finer although larger size carbon can be used; to 25 per cent by weight silicon metal, preferably of high purity, in a mesh size suitably of ---20 mesh or finer, preferably 2OO mesh; 5 to 30 per cent by weight of a hydraulic cement, for example, calcium aluminate and calcium silicate cements, and from O to 65 per cent, preferably 20 to 50 per cent by weight, of other refractory additives, such as refractory oxides and silicates, which are beneficial to bond strength and- /or oxidation resistance, including aluminum oxide, silica, zircon, pulverized firebrick and clays. Up to 20 per cent by weight of pitch may optionally be added to provide better bonding than obtained with the hydraulic cements at temperatures below the reaction temperature of carbon and silicon.

Refractory shaped articles such as tile and brick are prepared by blending the constituents with water, for example 12 to 20 per cent, suitably in a cement mixer; a small bowl type for small batches or a large paddle mixer for larger quantities. The mix is then cast into molds with, for example, a 9 X 2% inch cavity 4% inch deep. The shaped articles are air set, for example, overnight and oven dried at about 200F for 2 or more days to dry out sufficiently for shipment and use.

Firing of the shapes takes place on use in furnaces at high temperatures. Typical firing carried out on tests of brick specimens was at 2550F, a 5 hour hold, based on ASTM C 1 13-68, Schedule B. Bulk density, modulus of rupture, compressive strength and linear change was determined at room temperature. The final weight loss was used to determine carbon losses, correcting for normal firing weight losses with castables and calcining of clays. This exposure of five sides in an oxidizing kiln provides the most severe test conditions for our novel compositions.

DESCRIPTION OF PREFERRED EMBODIMENTS The tables show carbon and graphite raw materials in quantities of to 80 per cent by weight of the whole, but the carbon content indicated below the compositions is based on the known ash content of the individual carbonaceous constituents.

Formulations of carbon and graphite with silicon and calcium aluminate cements are shown in Table I. Without silicon, such formulations would lose all structural integrity on firing due to oxidation. With silicon, as shown in Table I, good strength properties are obtained, with decreasing carbon loss due to oxidation and generally increasing strength as silicon is'increased. The use of cokes instead of graphite (No. 4), or inclusion of larger grain sizings (No. 5), appear to lower effectiveness, but a useful refractory is represented by all formulations of Table I.

Carbon contents above 80 per cent are not feasible because of the desirability of at least 10 per cent silicon in the high carbon range and at least 10 per cent calcium aluminate cement to provide adequate initial strength for the normal requirements of a castable. The preferred cement used is of the refractory calcium aluminate type having up to 35 per cent calcium oxide and at least 40 per cent aluminum oxide.

Silicon contents of 5 per cent and above are useful, but above 20 per cent is not necessary and add considerable expense to the formulation. With carbon contents above 50 per cent it is preferable to have at least 10 per cent silicon. We have found that 20 mesh silicon is effective, but -2OO mesh is better for increased reactivity. The silicon should have no more than 3 per cent impurities, but if as much as 25 per cent impure it will retain some effectiveness.

Fine oxide addition increases strength with lower silicon contents, thereby decreasing cost, as shown in Table II. No. l in Table II has no silicon, and the carbon was essentially burned out although the high inorganic content held the samples together. Silica flour (Nos. 2, 3, 4), pulverized fire brick (No. 5), and milled zircon additions (Nos. 6, 7, 8) all resulted in high strengths with 5 to 12 /2 per cent silicon. These additions should all be of 30 mesh. Raw clays can be used but tend to make castables too plastic for ease of pouring.

Table III shows blends of high alumina with carbon, silicon, calcium aluminate and Portland (calcium silicate) cements. The alumina raw material in this case was calcined South American refractory grade bauxite, but any high alumina aggregate can be used. This combination is particularly effective for resistance to iron and steel slags. Calcined flint clays and other coarse re-' fractory aggregates have also been used. In all cases, a

refracto castable containing carbon or ra hite 's provi d to make available t e r a van f Ihg gnly preparation of the castable required prior to hot metal exposure is a dry-out, or a cure preferably at aboutitiODw if pitch is present (Nos. 5 and 7 in Table III).

Percent By Weight Natural Flake Graphite 8; Finer 40 Natural Flake Graphite V4" & Finer 60 45 Natural Flake Graphite 35 mesh 20 25 65 Calcined Coal 8t Finer 40 Coke Breeze /4" & Finer 20 20 Carbon Fines 0 mesh I0 Silicon. mesh 10 20 20 I0 I0 Calcium Aluminate Cement l0 l0 I5 20 20 Carbon Content 56 49 46 59 59 PROPERTIES 2550F FIRE: l 2 3 4 5 Bulk Density lbs/cu. ft. 73 86 90 63 62 Modulus of Rupture psi 200 450 670 I 90 Compressive Strength psi 950 I700 350 400 Shrinkage 7! by weight l0 0 1.0 2.0 2.2 Carbon Loss k by weight 38 6 4 53 48 TABLE II EFFECT OF FINE OXIDE ADDITION Percent By Weight Natu al Flake Graphite V." & Finer 50 45 55 45 55 40 45 Carbon or Graphite Fines mesh l2.5 l5 12.5 I0 10 l2.5 Silicon 20 mesh 0 5 I0 I25 l0 l0 I0 I25 Calcium Aluminate Cement l2.5 l0 l5 l0 l5 l0 10 IO Pulverized Brick 2Q Silica Flour 25 25 20 2O Milled Zircon 30 o Carbon Content 42 39 40 39 35 28 40 PROPERTIES 2550F FIRE: l 2 3 4 5 6 7 8 Bulk Density lbs/cu. ft. 68 87 93 92 97 109 I19 99 Modulus of Rupture psi I00 I90 300 900 590 770 950 700 Compressive Strength psi 300 I600 I300 2l0O 2l00 4500 4800 I200 Shrinkage 1 by weight l.4 l.l 0.2 0.8 0.5 1.6 L0 0.3 Carbon Loss "k by weight 80 32 23 ll 4 ll 4 l4 TABLE III BLENDS OF HIGH ALUMINA & CARBON WITH SILICON Percent By Weight I 2 3 4 5 6 7 Natural Flake Graphite V4" & Finer 35 15 25 I9 2O Calcined Coal 34" & Finer 25 Coke Breeze A" & Finer I9 20 20 Graphite or Carbon Fines 35 mesh 20 I0 I0 Pellet Pitch 5 5 Silicon 20 mesh 0 5 5 l0 9 l0 l0 Calcium Aluminate Cement l5 l0 l0 l5 I9 20 Calcined Refractory Bauxite V4" & Finer 40 45 30 28 25 25 Calcined Refractory Bauxite 30 mesh l0 I0 Ball Clay l0 5 5 l0 Portland Cement 20 Carbon Content 25 l6 I9 25 35 38 37 PROPERTIES 2550F FIRE: l 2 3 4 5 6 7 Bulk Density lbs/cu. ft. 99 H5 I14 I12 90 85 85 Modulus of Rupture psi I 6l0 400 400 220 I53 I70 Compressive Strength psi I50 I220 I280 2000 -75(.I 520 900 Shrinkage 1 by weight 0.9 0.7 0 0.6 0.2 0.4 0.6 76 32 2l 8 26 38 30 Carbon Loss 94 by weight We claim:

1. A composition suitable for making shaped refractory articles consisting essentially of particles of carbon metal in at least 5 per cent by weight, and pitch from in from 20-80 per cent by weight. a hydraulic cement 0-20 per cent by weight. in from 5-30 per cent by weight, particles of a refrac- 2. The composition of claim I in which silicon is prestory oxide or silicate in 0-65 per cent by weight, silicon ent in 5-25 per cent by weight.

5. The composition of claim 1 in which pitch is present and the aluminum oxide is present as refractory calcined bauxite.

6. A refractory shaped article consisting essentially of a carbon concrete consisting essentially of from 20-80 per cent by weight of carbon particles and from 5-25 per cent by weight of particles of silicon bonded together by a calcium alummate or calcium silicate cement. 

1. A COMPOSITION SUITABLE FOR MAKING SHAPED REFRACTORY ARTICLES CONSISTING ESSENTIALLY OF PARTICLES OF CARBON IN FROM 20-80 PER CENT BY WEIGHT, A HYDRAULIC CEMENT IN FROM 5-30 PER CENT BY WEIGHT, PARTICLES OF A REFRACTORY OXIDE OR SILICATE IN 0-65 PER CENT BY WEIGHT, SILICON METAL IN AT LEAST 5 PER CENT BY WEIGHT, AND PITCH FROM 0-20 PER CENT BY WEIGHT.
 2. The composition of claim 1 in which silicon is present in 5-25 per cent by weight.
 3. The composition of claim 1 in which silicon is present in at least 10 per cent by weight and calcium aluminate cement is present in at least 10 per cent by weight.
 4. The composition of claim 1 in which aluminum oxide, silica, zircon, pulverized firebrick, clay, or mixtures thereof are present in 20-50 per cent by weight.
 5. The composition of claim 1 in which pitch is present and the aluminum oxide is present as refractory calcined bauxite.
 6. A refractory shaped article consisting essentially of a carbon concrete consisting essentially of from 20-80 per cent by weight of carbon particles and from 5-25 per cent by weight of particles of silicon bonded together by a calcium aluminate or calcium silicate cement. 